JP6290785B2 - Moisture curable composition - Google Patents

Description

  The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. It relates to the curable composition containing this.

  An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property of being obtained.

  Among these polymers having a reactive silicon group, an organic polymer whose main chain skeleton is a polyoxyalkylene polymer has been disclosed in Patent Document 1 and the like, and has already been industrially produced, and a sealing material, Widely used in applications such as adhesives and paints.

  In particular, a curable composition containing a polyoxyalkylene polymer having a reactive silicon group and a polyacrylate polymer having a reactive silicon group is excellent in weather resistance, heat resistance, adhesiveness, etc. This technique is disclosed in Patent Document 2 and the like.

  On the other hand, an organic polymer having a reactive silicon group containing three hydrolyzable groups such as a trialkoxysilyl group is known to be excellent in rapid curability and disclosed in Patent Document 3 and the like.

JP-A-52-73998 JP-A-11-130931 (US6552118) JP 2005-502737 Gazette

  However, even when the curable composition described in Patent Document 2 is used, the weather resistance is not sufficient, and improvement has been desired. Further, the curable composition described in Patent Document 3 has a tendency that the cured product has a high modulus and a low elongation. The present invention is a curable composition comprising as a main component a (meth) acrylic acid ester-based polymer having a reactive silicon group, and has a low viscosity and quick curability, while being excellent in the weather resistance of the cured product. Another object of the present invention is to provide a curable composition having low modulus and high elongation properties.

  As a result of intensive studies to solve such problems, the present inventor has a specific number average molecular weight having a reactive silicon group formed by bonding three hydroxyl groups or hydrolyzable groups per silicon atom. In the curable composition containing (meth) acrylic acid ester polymer (A) as a main component and further containing a polyoxyalkylene polymer (B) having a reactive silicon group, 1 of component (A) It was found that by setting the number of reactive silicon groups per molecule to a specific amount, it is possible to obtain a curable composition having a low modulus cured product property while being excellent in weather resistance, workability, and fast curability, The present invention has been completed.

That is, the present invention
(1). A curable composition containing an organic polymer (I) having a silicon-containing group that can be crosslinked by forming a siloxane bond,
As a component (I), a silicon-containing group having a number average molecular weight of 1,000 to 10,000 and capable of crosslinking by forming a siloxane bond is represented by the general formula (1):
-SiX ₃ (1)
In the formula, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different from each other. A (meth) acrylic acid ester polymer (A) having ˜1.5 and a polyoxyalkylene polymer (B) having a silicon-containing group capable of crosslinking by forming a siloxane bond, A curable composition, wherein the weight percentage of the component (A) is from 51 to 99% by weight relative to the total weight of the component (I) in the curable composition;
(2). The silicon-containing group of the polyoxyalkylene polymer (B) has the general formula (2):
-SiR ¹ X ₂ (2)
Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. R ′ is a hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and X is the same as described above, X in the above may be the same or different.) The curable composition according to (1),
(3). The curable composition according to (1) or (2), wherein the main chain skeleton of the polyoxyalkylene polymer (B) is polypropylene oxide,
(4). (A) The curable composition according to any one of (1) to (3), wherein the component is a (meth) acrylic acid ester polymer containing 10 wt% or more of an acrylic acid ester monomer unit,
(5). Furthermore, 0.01-5 weight part of silanol condensation catalysts (C) are contained with respect to 100 weight part of total amount of (A) component and (B) component, Any one of (1) to (4) characterized by the above-mentioned The curable composition according to
(6). Furthermore, 0.1 to 20 parts by weight of the silane coupling agent (D) is contained with respect to 100 parts by weight of the total amount of the components (A) and (B), any of (1) to (5) A curable composition according to claim 1,
(7). Furthermore, it contains 10 to 200 parts by weight of the plasticizer (E) with respect to 100 parts by weight of the total amount of the component (A) and the component (B), and the component (A), the component (B) and the plasticizer (E) The curable composition according to any one of (1) to (6), wherein the weight percent of the component (A) is 51 to 99 weight percent with respect to the total weight of
(8). A curable composition containing the component (A) and the component (B) and not containing the plasticizer (E), the weight percentage of the component (A) relative to the total weight of the components (A) and (B) The curable composition according to any one of (1) to (6), wherein the curable composition is 51 to 99% by weight,
(9). Furthermore, the filler (F) is contained in an amount of 10 to 500 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), according to any one of (1) to (8) Curable composition,
(10). (1) to a sealing material using the curable composition according to any one of (9),
(11). An adhesive comprising the curable composition according to any one of (1) to (9),
(12). (1) to a coating material using the curable composition according to any one of (9),
(13). (1) to (9) a waterproof coating film comprising the curable composition according to any one of
(14). (1) to (9), a curable composition according to any one of (9) is applied on a waterproof layer,
(15). A laminate obtained by applying the curable composition according to any one of (1) to (9) on a waterproof layer;
About.

  The curable composition of the present invention has excellent weather resistance of a cured product, low modulus and high elongation properties while having low viscosity and fast curability.

  The present invention will be described in detail below.

  The curable composition of the present invention contains an organic polymer (I) having a reactive silicon group.

  The main chain skeleton of the component (I) is not particularly limited, and those having various main chain skeletons can be used.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers. Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product Is more preferable because of its excellent cold resistance.

  The glass transition temperature of the organic polymer as component (I) is not particularly limited, but is preferably 20 ° C or lower, more preferably 0 ° C or lower, and particularly preferably -20 ° C or lower. . If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease. The glass transition temperature is a value obtained by DSC measurement.

  In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-component composition, and also in excellent adhesiveness. A polyoxyalkylene polymer is most preferred.

  On the other hand, the (meth) acrylic acid ester polymer is preferable because the cured product has excellent weather resistance.

  The main chain skeleton of the organic polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

  The reactive silicon group contained in the organic polymer having a reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is a group capable of crosslinking.

As the reactive silicon group, the general formula (3):
-SiR ² _3-a X _a (3)
(Wherein each of 3-a R ^{2 s} independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′ ) ₃ SiO— (wherein R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and a number of X is each Independently, it is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3).

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

That is, the general formula (4):
-SiR ² _3-a (OR ³ ) _a (4)
(Wherein each of 3-a R ^{2 s} independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′ ) ₃ SiO— (R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms), and a number of R ³ are each independently And a is a hydrocarbon group having 1 to 2 carbon atoms, and a is any one of 1, 2, and 3), and is preferably hydrolyzable and easy to handle.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and 2 or 3 is preferable from the viewpoint of curability. When two or more hydrolyzable groups or hydroxyl groups are bonded to the silicon atom, they may be the same or different. A reactive silicon group having three hydroxyl groups or hydrolyzable groups on a silicon atom has high activity and good curability, and is excellent in resilience, durability and creep resistance of the resulting cured product. Therefore, it is preferable. That is, the value of a in the general formula (3) and the general formula (4) is preferably 2 or 3, and more preferably 3, from the viewpoint of curability and restorability. On the other hand, a reactive silicon group having two hydroxyl groups or hydrolyzable groups on a silicon atom is preferable because it is excellent in storage stability and the obtained cured product has high elongation and high strength. That is, the value of a in the general formulas (3) and (4) is preferably 2 from the viewpoints of storage stability and physical properties of the cured product.

Specific examples of R ^{2 in} the above general formulas (3) and (4) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and a benzyl group. And a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group, or the like. Of these, a methyl group is particularly preferred.

  More specific examples of the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because of high activity and good curability. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. Further, triethoxysilyl group and diethoxymethylsilyl group are particularly preferable because the alcohol produced by the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

  Introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method can be mentioned.

  (B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Subsequently, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

  (B) An organic polymer containing an unsaturated group obtained in the same manner as in the method (a) is reacted with a compound having a mercapto group and a reactive silicon group.

  (C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

  Among the above methods, the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is high in a relatively short reaction time. It is preferable because a conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. , Methyldimethoxysilane, phenyldimethoxysilane, alkoxysilanes such as 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyldiacetoxysilane Examples thereof include, but are not limited to, acyloxysilanes such as: ketoximate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the obtained organic polymer has high curability, storage stability, elongation characteristics, and tensile strength. Trimethoxysilane is particularly preferable from the viewpoints of curability and restorability of the resulting curable composition.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may undergo a disproportionation reaction. As the disproportionation reaction proceeds, fairly dangerous compounds such as dimethoxysilane and tetrahydrosilane are produced. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups such as trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthesis method (b) or (c) may be used. preferable.

On the other hand, general formula (5):
H- (SiR ⁴ ₂ O) _m SiR ⁴ ₂ -R ⁵ -SiX ₃ (5)
(In the formula, X is the same as described above. 2 × m + 2 R ^{4 s} are each independently a hydrocarbon group or —OSi (R ″) ₃ (R ″ is independently from 1 carbon atom) And a hydrocarbon group having 1 to 20 carbon atoms, and from the viewpoint of availability and cost, it is preferably 1 to 8 carbon atoms. The hydrocarbon group is more preferably a hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ is a divalent organic group, and is divalent having 1 to 12 carbon atoms from the viewpoint of availability and cost. A divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable, and m is an integer of 0 to 19. 1 from the viewpoint of availability and cost) The disproportionation reaction does not proceed with the silane compound. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), the silane compound represented by the general formula (5) should be used. Is preferred. Specific examples of the silane compound represented by the general formula (5) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxy Silyl) propyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.

  The organic polymer having a reactive silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the average number of reactive silicon groups contained in the organic polymer is at least 0.5, preferably 1-5, more preferably 1.3-4, and even more preferably 1.5-3. If the average number of reactive silicon groups contained in the molecule is less than 0.5, the curability becomes insufficient and good rubber elastic behavior is hardly exhibited. The reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network chain length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

  These organic polymers having a reactive silicon group may be used alone or in combination of two or more.

<< ((Meth) acrylic acid ester polymer (A) >>
In the present invention, as the component (I), the silicon-containing group having a number average molecular weight of 1,000 to 10,000 and capable of crosslinking by forming a siloxane bond is represented by the general formula (1):
-SiX ₃ (1)
In the formula, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different from each other. A (meth) acrylic acid ester polymer (A) having ˜1.5 is used as an essential component.

The weight percent of component (A) relative to the total weight of component (I) in the curable composition is 51 to 99 weight percent, preferably 53 to 95 weight percent, more preferably 55 to 90 weight percent, and 57 to 80% by weight is more preferable, and 60 to 70% by weight is particularly preferable. When the weight percentage of the component (A) is less than 51 weight%, the fast curability and weather resistance may be insufficient. On the other hand, when the weight percentage of the component (A) exceeds 99 weight%, the workability may be deteriorated due to high viscosity, and the stretched physical properties of the cured product may be lowered.
Cured product that the weight percentage of component (A) relative to the total weight of component (A), component (B), and plasticizer (E) described later in the curable composition is 51 to 99% by weight. It is preferable because yellowing with time is difficult to occur, and it is more preferably 60 to 80% by weight.

  More specific examples of the reactive silicon group of the general formula (1) include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, ethoxydimethoxysilyl group, diethoxymethoxysilyl group, diisopropoxymethoxy. A silyl group is mentioned. A trimethoxysilyl group is particularly preferred because of its high activity and good curability. Further, the triethoxysilyl group is particularly preferable because the alcohol produced with the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

  The number average molecular weight of the component (A) is essential to be 1,000 to 10,000 in terms of polystyrene in GPC, more preferably 2,000 to 8,000, still more preferably 3,000 to 7 000, particularly preferably 4,000 to 6,000. When the number average molecular weight of the component (A) is less than 1,000, the elongation property of the cured product may be deteriorated. On the other hand, when the number average molecular weight of the component (A) exceeds 10,000, workability may deteriorate due to high viscosity.

  It is essential that the reactive silicon group contained in the component (A) is 0.5 to 1.5 on average in one molecule of the polymer, preferably 0.6 to 1.4, More preferably, the number is 0.7 to 1.3, still more preferably 0.8 to 1.2, and particularly preferably 0.9 to 1.1. If it is less than 0.5, the curability is lowered, and good rubber elastic behavior may be hardly exhibited. On the other hand, when the number exceeds 1.5, the cured product becomes hard, and the elongation property may decrease.

  The reactive silicon group contained in the component (A) is preferably present at the end of the side chain rather than at the end of the main chain of the polymer from the viewpoint of fast curing. Since the reactive silicon group can be easily introduced into the terminal of the side chain of the polymer, the component (A) is a monomer mixture containing an acrylate monomer having a silicon-containing group of the general formula (1) A polymer obtained by polymerization of is preferable.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, (meth) acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In the field construction type application, since it is required to have low viscosity and excellent workability, it is preferable to use an acrylate monomer. The proportion of acrylic acid ester monomer units in all monomer units is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more. . Among the acrylate monomers, butyl acrylate is particularly preferable because of its low viscosity and excellent workability. The proportion of butyl acrylate monomer units in all monomer units is preferably 10% by weight or more, more preferably 30% by weight or more, still more preferably 50% by weight or more, and particularly preferably 70% by weight or more.

  On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the alkyl group in the side chain in order to improve low temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40-50 / 20 by weight) 30/30 to 20). In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to perform by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a large degree of freedom in designing initiators and catalysts ( The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive silicon group include chain transfer described in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. A production method using a free radical polymerization method using an agent is disclosed. Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

  As a method for producing the (meth) acrylic acid ester-based polymer (A) having a reactive silicon group, a solution polymerization method is preferred because gelation due to the reaction of the reactive silicon group during polymerization is relatively difficult.

  The (meth) acrylic acid ester-based polymer having a reactive silicon group may be used alone or in combination of two or more.

A method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based polymer having a reactive silicon group and a polyoxyalkylene-based polymer having a reactive silicon group, which is a component (B) described later, is particularly Although proposed in Japanese Utility Model Laid-Open No. 59-122541, Japanese Patent Laid-Open No. 63-112642, Japanese Patent Laid-Open No. 6-172631, and Japanese Patent Laid-Open No. 11-116663, it is not particularly limited thereto. A preferred specific example has a reactive silicon group and a molecular chain substantially having the following general formula (6):
—CH ₂ —C (R ⁶ ) (COOR ⁷ ) — (6)
(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 7 carbon atoms) and a (meth) acrylic acid ester having an alkyl group having 1 to 7 carbon atoms A monomer unit and the following general formula (7):
—CH ₂ —C (R ⁶ ) (COOR ⁸ ) — (7)
(Wherein R ⁶ is the same as above, and R ⁸ represents an alkyl group having 8 or more carbon atoms) represented by a (meth) acrylate monomer unit having an alkyl group having 8 or more carbon atoms And a copolymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group.

As R ^{7 in the} general formula (6), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group and the like are 1 to 7, preferably 1 to 4, and more preferably 1 To 2 alkyl groups. The alkyl group R ⁷ may alone, or may be a mixture of two or more.

R ^{8 in the} general formula (7) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 8 or more carbon atoms, usually 8 to 30, preferably 8 There are 20 long-chain alkyl groups. The alkyl group of R ⁸ is similar to the case of R ^7, individually may or may be a mixture of two or more.

  The molecular chain of the (meth) acrylate polymer is substantially composed of monomer units of the formulas (6) and (7). The term “substantially” here means in the copolymer Means that the sum of the monomer units of formula (6) and formula (7) present in the formula exceeds 50% by weight. The sum of the monomer units of formula (6) and formula (7) is preferably 70% by weight or more.

  Further, the abundance ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight.

  Examples of monomer units other than those represented by formula (6) and formula (7) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, Monomers containing an amide group such as N-methylol methacrylamide, an epoxy group such as glycidyl acrylate and glycidyl methacrylate, and an amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene Monomer units derived from alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based polymer having a reactive silicon functional group, in the presence of an organic polymer having a reactive silicon group ( A method of polymerizing a meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

<< About the polyoxyalkylene polymer (B) >>
In the present invention, as the component (I), a polyoxyalkylene polymer (B) having a silicon-containing group that can be crosslinked by forming a siloxane bond is used as an essential component.

  The weight percent of the component (B) relative to the total weight of the component (I) in the curable composition is 1 to 49 weight percent, preferably 5 to 47 weight percent, more preferably 10 to 45 weight percent, and 20 to 20 weight percent. 43 weight% is further more preferable and 30 to 40 weight% is especially preferable. When the weight percentage of the component (B) is less than 1 weight%, workability may deteriorate due to high viscosity, and the stretched physical properties of the cured product may deteriorate. On the other hand, when the weight percentage of the component (B) exceeds 49 weight%, the fast curability and weather resistance may be insufficient.

As the reactive silicon group of the component (B), the general formula (2):
-SiR ¹ X ₂ (2)
Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. R ′ is a hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and X is the same as described above, X may be the same or different. From the viewpoint of storage stability and stretched physical properties of the cured product, it is preferable.

  More specific examples of the reactive silicon group of the general formula (2) include a dimethoxymethylsilyl group, a dimethoxyethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. A dimethoxymethylsilyl group is particularly preferred because of its high activity and good curability. In addition, the diethoxymethylsilyl group is particularly preferable because the alcohol produced with the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

The polyoxyalkylene polymer essentially has the general formula (8):
—R ⁹ —O— (8)
(Wherein R ⁹ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁹ in the general formula (8) is a carbon atom. A linear or branched alkylene group having 1 to 14 or 2 to 4 is preferable. Specific examples of the repeating unit represented by the general formula (8) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in sealants and the like, a polymer composed mainly of a propylene oxide polymer having a propylene oxide repeating unit of 50% by weight or more is amorphous or has a relatively low viscosity. It is preferable from the point.

  Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent 3,278,457, US Patent 3,278,458, US Patent 3,278,459, US Patent 3,427,256, US Patent 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

  A method for producing a polyoxyalkylene polymer having a reactive silicon group is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, JP-A-57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Killen polymer can be exemplified, but not particularly limited thereto.

  The above polyoxyalkylene polymers having a reactive silicon group may be used alone or in combination of two or more.

  The polymer of component (B) may be linear or branched, and its number average molecular weight is about 500 to 100,000, more preferably 1,000 to 50,000 in terms of polystyrene in GPC. Particularly preferred is 3,000 to 30,000, and most preferred is 10,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity. The molecular weight distribution (Mw / Mn) of the component (B) is preferably 1.6 or less because the viscosity of the composition is low and workability is good. The molecular weight distribution is more preferably 1.4 or less, and even more preferably 1.3 or less.

  In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, at least one reactive silicon group contained in the polymer of the component (B) on average in one polymer molecule. , Preferably 1.1 to 5, more preferably 1.2 to 3, further preferably 1.3 to 2.5, and particularly preferably 1.4 to 2. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network chain length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

<< Curable composition >>
In the curable composition of this invention, various compounding agents can be added according to the target physical property.

<< Silanol condensation catalyst (C) >>
In the curable composition of the present invention, a silanol condensation catalyst can be used as the component (C). The silanol condensation catalyst is not particularly limited, and examples thereof include a silanol condensation catalyst that promotes a reaction of a commonly used hydrolyzable silicon group. Specific examples include carboxylic acid metal salts such as tin 2-ethylhexanoate, tin versatate, and bismuth 2-ethylhexanoate; carboxylic acids such as 2-ethylhexanoic acid and versatic acid; dibutyltin dilaurate, dibutyltin maleate, Dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (Octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin Dimethoxide, dibutyltin bis Nonylphenoxide), dibutenyl tin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetate), reaction product of dibutyltin oxide and silicate compound, dialkyltin dicarboxylate such as dibutyltin dilaurate and silicate Tetravalent organotin compounds such as reactants with compounds, reactants of dibutyltin oxide and phthalates; tetraisopropoxytitanium, tetra-n-butoxytitanium, diisopropoxytitanium bis (acetylacetonate), diisopropoxy Organic titanates such as titanium bis (ethyl acetoacetate); aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate Organoaluminum compounds such as zirconium; zirconium compounds such as zirconium tetrakis (acetylacetonate); methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine Aliphatic primary amines such as laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, bis ( 2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine Aliphatic secondary amines such as ethyl stearylamine and butylstearylamine; Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; Aliphatic unsaturation such as triallylamine and oleylamine Amines; aromatic amines such as lauryl aniline, stearyl aniline, triphenylamine; and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, diethylenetriamine, triethylenetetramine, benzyl Amine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenedi Min, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4 0) Undecene-7 (DBU), 1,5-diazabicyclo (4,3,0) nonene-5 (DBN) and the like.

  The silanol condensation catalyst of component (C) is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B). It is used in the range of 5 to 3 parts by weight. If the blending amount is less than 0.01 parts by weight, the curability may not be sufficient. On the other hand, if the blending amount exceeds 5 parts by weight, the storage stability may decrease.

<< Silane coupling agent (D) >>
As the component (D), a silane coupling agent can be added to the curable composition of the present invention. Specific examples include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, and (isocyanatemethyl). Isocyanate group-containing silanes such as dimethoxymethylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriiso Propoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrime Xysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2- Aminoethyl) aminopropyltriisopropoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltri Ethoxysilane N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, etc. Amino group-containing silanes; Ketimine type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltri Mercapto group-containing silanes such as ethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. Epoxy group-containing silanes; carboxy such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Silanes; vinyl type unsaturated such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane It can be mentioned tris (3-trimethoxysilylpropyl) isocyanurate silanes such as isocyanurate; containing silanes; .gamma. halogen-containing silanes such as chloropropyl trimethoxy silane. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . Examples of the reaction product of the silane coupling agent include the reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, and partial condensates of various silane coupling agents.

  The silane coupling agent of component (D) is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 3 to 7 parts per 100 parts by weight of the total amount of components (A) and (B). Used in the range of parts by weight. If the blending amount is less than 0.1 parts by weight, the adhesion and storage stability may not be sufficient. On the other hand, if the blending amount exceeds 20 parts by weight, the elongation of the cured product may decrease, or the deep curability may not be sufficient.

<< Plasticizer (E) >>
A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

  Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000 to 1,000. 5,000. Most preferably, it is 1,000-3,000. If the molecular weight is less than 500, the plasticizer flows out with time due to heat or rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. On the other hand, when the molecular weight exceeds 15,000, the viscosity increases and workability deteriorates. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, is used, the number average molecular weight must be lower than that of the polymer of component (B).

  A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

  The plasticizer of the component (E) is in the range of 10 to 200 parts by weight, preferably 20 to 120 parts by weight, more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Used in. If the blending amount is less than 10 parts by weight, the plasticizing effect may not be sufficient. On the other hand, if the blending amount exceeds 200 parts by weight, the cured product properties may be deteriorated.

  On the other hand, when a plasticizer is blended, when the curable composition is applied on the asphalt waterproofing layer, the components in the asphalt easily migrate into the composition, or the relative (A) in the composition Since the weight% of a component decreases and yellowing of a coating film may occur, it is not preferable. Therefore, the plasticizer (E) is not blended so much, that is, blends less than 1 part by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and further blends less than 0.5 part by weight. In addition, it may be preferable not to blend substantially.

<< Filler (F) >>
A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as asbestos, glass fibers, and filaments.

  The filler of the component (F) is in the range of 10 to 500 parts by weight, preferably 50 to 300 parts by weight, more preferably 100 to 200 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Used in. If the amount is less than 10 parts by weight, the strength of the cured product may not be sufficient. On the other hand, if the blending amount exceeds 500 parts by weight, the elongation characteristics of the cured product may deteriorate.

<< Solvent >>
In the composition of the present invention, a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketone solvents, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. In the case of using a solvent, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. These solvents may be used alone or in combination of two or more.

  However, when the amount of the solvent is large, toxicity to the human body may be increased, and volume shrinkage of the cured product may be observed. Therefore, the blending amount of the solvent is preferably less than 1 part by weight, more preferably less than 0.1 part by weight based on 100 parts by weight of the total amount of the component (A) and the component (B). Most preferably, it is substantially free of.

<< Thixotropic agent >>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B).

<< Antioxidant >>
An antioxidant (antiaging agent) can be used in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 144, Tinuvin 292, Tinuvin 622LD, Tinuvin 744, Tinuvin 765, Tinuvin 770, CHIMASSORB 944LD (all of which are manufactured by BASF); SABOSTAB UV 119 (manufactured by SABO); -62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 (all manufactured by ADEKA Corporation); SANOL LS-770, SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS- The hindered amine light stabilizer shown in 1114, Sanol LS-744 (all are the Sankyo Co., Ltd. product) etc. can also be used.

  Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). Part.

<< light stabilizer >>
A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). Part. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 144, Tinuvin 292, Tinuvin 622LD, Tinuvin 765, CHIMASSORB 944LD (all manufactured by BASF); SABOSTAB UV 119 (manufactured by SABO); Adekastab LA-52, Adekastab LA-62, Examples include light stabilizers such as ADK STAB LA-63 (all manufactured by ADEKA Corporation); SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114 (all manufactured by Sankyo Corporation) it can.

<< UV absorber >>
An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Part. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

<< Other various additives >>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, epoxy resins, epoxy resin curing agents, photocurable materials, oxygen curable materials, silanol-containing compounds, tackifiers, thermoplastic elastomers, flame retardants, and curing modifiers. , Radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, ant-proofing agents, fungicides, and the like. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

<< Method for adjusting curable composition >>
The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl By adding an alkoxysilane compound such as methyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane, the storage stability is further improved.

  The amount of silicon compound capable of reacting with water, such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0 with respect to 100 parts by weight of the total amount of components (A) and (B). The range of 5 to 10 parts by weight is preferred.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

  When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

<< Usage >>
The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. It can be used for coating materials and waterproofing coating films. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility, adhesion, and weather resistance, among these, as a sealing material, an adhesive, a coating material, a waterproof coating material, More preferably, it is used.

Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, primers, electromagnetic shielding conductive materials , Heat conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), automotive parts, It can be used for various applications such as liquid sealants used in electrical parts and various machine parts.
Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. .
Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

<Waterproofing method and laminate>
In the present invention, the following waterproofing method and a laminate laminated by the method are disclosed.

  The waterproofing method of the present invention is a waterproofing method in which a curable composition containing the components (A) and (B) as essential components is applied onto a waterproof layer.

  The waterproof layer is not particularly limited, and examples thereof include an asphalt waterproof layer, a sheet waterproof layer, and a coating waterproof layer.

  In particular, the curable composition of the present invention containing the component (A) and the component (B) in a weight ratio of (A) / (B) = 51/49 to 99/1 is applied on the asphalt waterproofing layer. However, the coating film is preferable because the yellowing with time is small, and an inexpensive and highly reliable waterproof layer can be obtained.

  The weight ratio of the component (A) to the component (B) is preferably (A) / (B) = 53/47 to 95/5, more preferably (A) / (B) = 55/45 to 90/10. (A) / (B) = 57/43 to 80/20 is more preferable, and (A) / (B) = 60/40 to 70/30 is particularly preferable.

  When the weight percentage of the component (B) is less than 1 weight%, workability may deteriorate due to high viscosity, and the stretched physical properties of the cured product may deteriorate. On the other hand, when the weight percentage of the component (B) exceeds 49 weight%, the fast curability and weather resistance may be insufficient, or the yellowing of the coating film when applied on the asphalt waterproofing layer may be significant. There is.

  Moreover, when the composition of this invention contains a plasticizer, a coating film may become yellow easily. In order to suppress yellowing of the coating film, the amount of the plasticizer in the composition of the present invention is preferably small, and more preferably no plasticizer is contained.

  In this case, the weight ratio of the component (A) to the component (B) is 51/49 to 99/1, and the plasticizer (100 parts by weight of the total amount of the component (A) and the component (B) E) is preferably 0 to 200 parts by weight, more preferably plasticizer (E) is 0 to 120 parts by weight, and plasticizer (E) is further preferably 0 to 80 parts by weight, It is particularly preferred that no plasticizer (E) is contained.

  Various types of commercially available asphalt roofing can be used as the asphalt waterproofing layer. Specifically, asphalt roofing (asphalt roofing, stretch roofing, modified asphalt roofing) constructed by thermal method, modified asphalt roofing, modified asphalt roofing constructed by torch method are pasted with room temperature type asphalt coating material Asphalt roofing with a cooling method applied, and asphalt roofing with a coating method in which liquid asphalt is reinforced with a reinforcing material.

  The sheet waterproof layer is not particularly limited, and various commercially available sheet waterproof layers can be used. Specific examples include a vulcanized rubber sheet, a vinyl chloride resin sheet, an ethylene vinyl acetate sheet, and a polyolefin sheet.

  The coating waterproof layer is not particularly limited, and various commercially available waterproof coating materials can be used. Specifically, urethane rubber-based coating film waterproofing material, rubber asphalt-based coating film waterproofing material, acrylic rubber-based coating film waterproofing material, FRP-based coating film waterproofing material, polymer cement-based coating film waterproofing material and the like.

  The site | part of the building where each waterproofing method of this invention is applied is not specifically limited, It can construct in the place where waterproofing is required. Specifically, places that need waterproofing against rainwater, such as roofs, rooftops, balconies, verandas, open corridors, artificial grounds, and outer walls; places that need waterproofing against groundwater, such as underground parts (underground shopping habits, basements); Locations that require waterproofing against domestic water, such as bathrooms, kitchens, toilets, water tanks, sewage tanks, and firefighting tanks; places that require waterproofing against industrial water, such as heat storage layers, miscellaneous drainage tanks, artificial ponds, pools, and wastewater treatment tanks Is mentioned. Since each waterproofing method of the present invention provides a waterproof layer with high waterproof reliability, among these, it is particularly useful when used on a roof or a rooftop.

  The foundation layer to which each waterproofing method of the present invention is applied is not particularly limited, and can be applied to various cases such as forming a new waterproof layer, renovating an existing waterproof layer, and waterproofing indoors. Specifically, concrete base such as cast-in-place concrete, reinforced concrete, precast concrete, ALC, mortar, plaster, siding board, slate, solid wood, plywood, particle board, oriented strand board, fiber board, lumbar core board, Examples include single-layer laminates, wood bases such as field boards, metal bases such as steel purlins, metal panels, and deck plates.

  In each waterproofing method of the present invention, the construction method on the base is not particularly limited, and construction can be performed by a known method. For example, a ventilation cushioning sheet method, a fiber reinforced adhesion method, a general adhesion method, and the like are applicable to the method of the present invention.

  Although each waterproofing method of the present invention is effective in new construction and renovation, the waterproofing method of the present invention is particularly effective in the case of refurbishing an existing exposed finish asphalt waterproofing layer.

Examples of the construction surface that can be applied in each waterproofing method of the present invention include an existing or newly built concrete slab surface, an existing concrete pressing waterproof layer surface, an existing sand-finished waterproofing layer surface, a heat insulating pressing waterproof layer surface, and the like.
In order to suppress the contamination of the asphalt waterproofing layer due to the migration of the solvent and plasticizer in the curable composition, it is necessary to reduce the amount of solvent and plasticizer used. It is necessary to achieve both low viscosity and high strength.

  Moreover, the waterproof laminated structure constructed | assembled by the construction method of this invention is not specifically limited, It constructs by selecting suitably from a well-known waterproof structure. For example, a laminated structure similar to the exposed waterproof construction method, concrete holding waterproof construction method, heat insulation exposed waterproof construction method, and concrete holding insulation waterproof construction method can be applied to the construction method of the present invention.

  Specific examples of the present invention will be described below, but the present invention is not limited to the following examples.

  In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). Tosoh HLC-8120GPC was used as the liquid feeding system, the column was TOS-GEL H type manufactured by Tosoh, and the solvent was measured using THF.

(Synthesis Example 1)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. The butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylic acid ester-based polymer <A-1> having a reactive silicon group. It was.

  n-butyl acrylate: 65.5 parts by weight, 2-ethylhexyl acrylate: 30 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 4.5 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

  The number average molecular weight determined by GPC was 5,700. The number of trimethoxysilyl groups introduced per polymer molecule was 1.0 on average.

(Synthesis Example 2)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. A butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylate polymer <A-2> having a reactive silicon group. It was.

  n-butyl acrylate: 95.5 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 4.5 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

  The number average molecular weight determined by GPC was 5,900. The number of trimethoxysilyl groups introduced per polymer molecule was 1.0 on average.

(Comparative Synthesis Example 1)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. A butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylate polymer <X-1> having a reactive silicon group. It was.

  n-butyl acrylate: 68.3 parts by weight, 2-ethylhexyl acrylate: 30 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 1.7 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 0.3 parts by weight.

  The number average molecular weight measured by GPC was 15,000. The number of trimethoxysilyl groups introduced per polymer molecule was 1.0 on average.

(Comparative Synthesis Example 2)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. The butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylate polymer <X-2> having a reactive silicon group. It was.

  n-butyl acrylate: 65.7 parts by weight, 2-ethylhexyl acrylate: 30 parts by weight, γ-methacryloyloxypropylmethyldimethoxysilane: 4.3 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

  The number average molecular weight determined by GPC was 5,700. The average number of methyldimethoxysilyl groups introduced per molecule of the polymer was 1.0.

(Comparative Synthesis Example 3)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. A butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylic acid ester-based polymer <X-3> having a reactive silicon group. It was.

  n-butyl acrylate: 61.5 parts by weight, 2-ethylhexyl acrylate: 30 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 8.5 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

  The number average molecular weight by GPC measurement was 5,600. The number of trimethoxysilyl groups introduced per polymer molecule was 1.8 on average.

(Comparative Synthesis Example 4)
Isobutanol heated to 105 ° C. in a reaction vessel was dissolved in the following (meth) acrylate monomer mixture and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator. A butanol solution was added dropwise over 5 hours, followed by “post-polymerization” for 1 hour, and then the solvent was distilled off to obtain a (meth) acrylic acid ester-based polymer <X-4> having a reactive silicon group. It was.

  n-butyl acrylate: 68.7 parts by weight, 2-ethylhexyl acrylate: 30 parts by weight, γ-methacryloyloxypropyltrimethoxysilane: 1.3 parts by weight, 2,2′-azobis (2-methylbutyronitrile): 2.5 parts by weight.

  The number average molecular weight determined by GPC was 5,800. The average number of trimethoxysilyl groups introduced per molecule of the polymer was 0.3.

(Synthesis Example 3)
Polymerization of propylene oxide was carried out using a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a polypropylene oxide having a number average molecular weight of 16,000. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polypropylene oxide to distill off the methanol, and a 1.2-fold equivalent of allyl chloride was added to remove the terminal hydroxyl group. Converted to an allyl group. As a result, polypropylene oxide having a number average molecular weight of 16,000 having an allyl group at the end was obtained.

After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain purified allyl group-terminated polypropylene oxide. 100 parts by weight of this polymer was reacted with 1.3 parts by weight of methyldimethoxysilane for 5 hours at 90 ° C. using 150 ppm of an isopropanol solution containing 3 wt% of platinum as a platinum vinylsiloxane complex as a catalyst, and then methyldimethoxysilyl group-terminated polypropylene oxide. (B-1) was obtained. ^{As a} result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal methyldimethoxysilyl groups was 1.2 on average per molecule.

(Synthesis Example 4)
Synthesis Example 3 using a hydroxyl-terminated polypropylene oxide having a number average molecular weight of 28,000 obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator. Allyl-terminated polypropylene oxide was obtained by the same procedure. This allyl-terminated polypropylene oxide is reacted with 1.0 part by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 3, and a polyoxypropylene polymer having an average of 1.5 methyldimethoxysilyl groups at the ends ( B-2) was obtained.

(Examples 1-4, Comparative Examples 1-6)
According to the formulation shown in Table 1, reactive silicon group-containing (meth) acrylic acid ester-based polymers (A-1 to A-2, X-1 to X-4), reactive silicon group-containing polyoxyalkylene-based polymers After blending (B-1 to B-2) and Actol 21-56 (Mitsui Chemicals, polypropylene glycol having a number average molecular weight of 2,000) as a plasticizer and mixing them well, the viscosity of each composition was Using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd., rotor No. 4), the measurement was performed under the conditions of 23 ° C. at a rotational speed of 12 rpm. When the viscosity value is less than 5 Pa · s, it is indicated as “Good”, and when it is 5 Pa · s or more, “No”.

(Examples 5-8, Comparative Examples 7-10)
According to the prescription shown in Table 2 below for the composition having a low viscosity of less than 5 Pa · s in the viscosity measurement, a filler, a thixotropic agent, an ultraviolet absorber, a light stabilizer, and an adhesion promoter. Each of the dehydrating agent and the curing catalyst is weighed and kneaded under a dehydrating condition in a substantially moisture-free state, and then sealed in a moisture-proof container. Got. The one-component compositions in Table 2 were discharged from each container during use and evaluated as described below.

In addition, the various compounding agents shown below were used.
<Filling material> White gloss flower CCR (manufactured by Shiraishi Kogyo Co., Ltd., colloidal calcium carbonate), Taipei R-820 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide)
<Thixotropic agent> Disparon 6500 (manufactured by Enomoto Kasei, amide wax-based thixotropic agent)
<Ultraviolet absorber> Tinuvin 326 (manufactured by BASF)
<Light stabilizer> Tinuvin 770 (manufactured by BASF)
<Adhesiveness imparting agent> A-1120 (manufactured by Momentive Performance Materials, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane)
<Dehydrating agent> A-171 (Momentive Performance Materials, vinyltrimethoxysilane)
<Curing catalyst> Neostan U-220H (manufactured by Nitto Kasei, dibutyltin bisacetylacetonate).

(Curing test)
The curability (skinning time) of each composition in Table 2 was evaluated in the following manner. Each composition was filled in a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat surface. This time was set as the curing start time, the surface was touched with a spatula, and the time when the composition did not adhere to the spatula was measured as the skinning time. The skinning time was measured under the condition of 23 ° C./50% RH. The results are shown in Table 2.

(Elongation properties of cured product)
Each composition of Table 2 was filled into a 3 mm thick mold using a spatula, and the surface was adjusted to a flat surface. This was cured at 23 ° C./50% RH × 3 days + 50 ° C. × 4 days to obtain a cured product having a thickness of about 3 mm. This cured product was punched into a No. 3 dumbbell mold, subjected to a tensile test at a pulling speed of 200 mm / min, and measured for elongation at break (%). The results are shown in Table 2.

(Weather resistance test)
Each composition of Table 2 was filled into a 3 mm thick mold using a spatula, and the surface was adjusted to a flat surface. This was cured at 23 ° C./50% RH for 7 days to prepare a cured sheet having a thickness of about 3 mm, and a weather resistance test was performed. The weather resistance test was carried out by putting a sample in Sunshine Super Long Life Weather Meter WEL-SUN-HC manufactured by Suga Test Instruments Co., Ltd. using sunshine carbon as a light source and setting the black panel temperature to 63 ° C. It was taken out after 3000 hours, and the surface of the cured product was visually observed to check for cracks. When there was no crack, it was set as (circle), and when the crack existed, it was set as x.

  From the test results shown in Tables 1 and 2, the (meth) acrylic acid ester polymer (A) having a reactive silicon group and the polyoxyalkylene polymer (B) having a reactive silicon group are represented by (A) / ( B) It can be seen that the compositions of Examples 1 to 8 contained at a weight ratio of 51/49 to 99/1 exhibit high weather resistance, fast curability, and high elongation properties while having low viscosity.

(Example 9, Comparative Examples 11-13)
In accordance with the formulation shown in Table 3 below, the reactive silicon group-containing (meth) acrylic acid ester polymer (A-1), the reactive silicon group-containing polyoxyalkylene polymer (B-1), a filler, and Each of the curing catalyst was weighed and kneaded under a dehydrating condition in a substantially moisture-free state, and then sealed in a moisture-proof container to obtain a one-pack curable composition. The one-component compositions in Table 3 were discharged from each container at the time of use, and evaluated later.

In addition, the various compounding agents shown below were used.
<Filler> Q3T (manufactured by Hubercarb, surface-treated heavy calcium carbonate), Taipei R-820 (manufactured by Ishihara Sangyo, titanium oxide)
<Curing catalyst> Versatic 10 (manufactured by Japan Epoxy Resin, neodecanoic acid), diethylaminopropylamine (manufactured by Wako Pure Chemical Industries).

(Workability)
Each composition of Table 3 was applied using a brush, and the workability was evaluated based on the ease of application. When the coating is less likely to be rubbed, it is indicated as ○, and when it is difficult to paint due to high viscosity, it is indicated as ×. The results are shown in Table 3.

(Yellowing on asphalt sheet)
Each composition of Table 3 was apply | coated so that it might become thickness 0.5mm on an asphalt waterproofing sheet. This coating film was cured at 23 ° C./50% RH, and after 1 day and 28 days, the b value was measured using a color difference meter. Table 3 shows the increase in b value after 28 days (b value after 28 days minus b value after 1 day).

  From the test results in Table 3, the (meth) acrylic acid ester polymer (A) having a reactive silicon group and the polyoxyalkylene polymer (B) having a reactive silicon group are (A) / (B) = It can be seen that the composition of Example 9 contained at a weight ratio of 51/49 to 99/1 has little workability on the asphalt waterproofing layer while having good workability that is easy to apply.

  The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. It can be used for coating materials and waterproofing coating films. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility, adhesion, and weather resistance, among these, as a sealing material, an adhesive, a coating material, a waterproof coating material, More preferably, it is used.

Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, primers, electromagnetic shielding conductive materials , Heat conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), automotive parts, It can be used for various applications such as liquid sealants used in electrical parts and various machine parts.
Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. .
Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

Claims (17)

A curable composition containing an organic polymer (I) having a silicon-containing group that can be crosslinked by forming a siloxane bond,
As a component (I), a silicon-containing group having a number average molecular weight of 1,000 to 10,000 and capable of crosslinking by forming a siloxane bond is represented by the general formula (1):
-SiX ₃ (1)
(Wherein, X represents a hydroxyl group or a hydrolyzable group, three X may be identical to each other, or different may be) the only group represented by average per molecule 0. Containing (meth) acrylic acid ester polymer (A) having 5 to 1.5, and polyoxyalkylene polymer (B) having a silicon-containing group that can be crosslinked by forming a siloxane bond, The curable composition, wherein the weight percentage of the component (A) is from 51 to 99% by weight relative to the total weight of the component (I) in the curable composition. The silicon-containing group of the polyoxyalkylene polymer (B) has the general formula (2):
-SiR ¹ X ₂ (2)
(In the formula, R ¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by (R ′) ₃ SiO—. R ′ is a hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and X is the same as described above, The curable composition according to claim 1, wherein X's may be the same or different.   The curable composition according to claim 1 or 2, wherein the main chain skeleton of the polyoxyalkylene polymer (B) is polypropylene oxide.   The curable composition according to any one of claims 1 to 3, wherein the component (A) is a (meth) acrylic acid ester polymer containing 10 wt% or more of an acrylic acid ester monomer unit.   Furthermore, 0.01-5 weight part of silanol condensation catalysts (C) are contained with respect to 100 weight part of total amount of (A) component and (B) component, The claim 1 characterized by the above-mentioned. Curable composition.   Furthermore, 0.1-20 weight part of silane coupling agents (D) are contained with respect to 100 weight part of total amount of (A) component and (B) component, In any one of Claim 1 to 5 characterized by the above-mentioned. The curable composition as described.   Furthermore, it contains 10 to 200 parts by weight of the plasticizer (E) with respect to 100 parts by weight of the total amount of the components (A) and (B), and the component (A), the component (B) and the plasticizer (E) The curable composition according to any one of claims 1 to 6, wherein the weight percentage of the component (A) is 51 to 99 weight% with respect to the total weight. The curable composition according to claim 7, wherein the component (E) is a polyether polyol.   A curable composition containing the component (A) and the component (B) and not containing the plasticizer (E), the weight percentage of the component (A) relative to the total weight of the components (A) and (B) The curable composition according to any one of claims 1 to 6, wherein the curable composition is 51 to 99% by weight. Furthermore, 10-500 weight part of fillers (F) are contained with respect to 100 weight part of total amounts of (A) component and (B) component, Curability in any one of Claim 1 to 9 characterized by the above-mentioned. Composition. The component (A) comprises (meth) acrylic acid n-butyl monomer unit, γ- (methacryloyloxypropyl) trimethoxysilane monomer unit, methacryloyloxymethyltrimethoxysilane monomer unit, and methacryloyloxy. A copolymer comprising one or more monomer units selected from the group consisting of methyltriethoxysilane monomer units, or
(Meth) acrylic acid n-butyl monomer unit, (meth) acrylic acid 2-ethylhexyl monomer unit, γ- (methacryloyloxypropyl) trimethoxysilane monomer unit, methacryloyloxymethyltrimethoxysilane single unit The copolymer consisting of a monomer unit and one or more monomer units selected from the group consisting of a methacryloyloxymethyltriethoxysilane monomer unit. Curable composition. The sealing material which uses the curable composition in any one of Claim 1 to 11 . An adhesive comprising the curable composition according to any one of claims 1 to 11 . The coating material which uses the curable composition in any one of Claim 1 to 11 . A waterproofing coating film comprising the curable composition according to any one of claims 1 to 11 . A waterproofing method comprising applying the curable composition according to any one of claims 1 to 11 on a waterproof layer. The laminated body obtained by apply | coating the curable composition in any one of Claim 1 to 11 on a waterproof layer.